CN114752056A - Device and method for repeatedly and stably producing polyaryletherketone with narrow molecular weight distribution - Google Patents
Device and method for repeatedly and stably producing polyaryletherketone with narrow molecular weight distribution Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000009826 distribution Methods 0.000 title claims abstract description 29
- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000000523 sample Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 14
- 239000010980 sapphire Substances 0.000 claims abstract description 14
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 10
- 230000008859 change Effects 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- HKCNCNXZAZPKDZ-UHFFFAOYSA-N (4,4-difluorocyclohexa-1,5-dien-1-yl)-phenylmethanone Chemical compound C1=CC(F)(F)CC=C1C(=O)C1=CC=CC=C1 HKCNCNXZAZPKDZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 239000013307 optical fiber Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 42
- 239000004696 Poly ether ether ketone Substances 0.000 description 37
- 229920002530 polyetherether ketone Polymers 0.000 description 37
- 229920000642 polymer Polymers 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000001914 filtration Methods 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Polyethers (AREA)
Abstract
The invention discloses a device and a method for repeatedly and stably producing polyaryletherketone with narrow molecular weight distribution.A polymerization reaction kettle is provided with a sapphire window, the outside of the sapphire window is matched with 1 online infrared spectrum probe, the online infrared spectrum probe is connected with an infrared spectrometer through an optical fiber, an online pH analyzer is arranged in the polymerization reaction kettle, a reaction solvent diphenylsulfone is added into the polymerization reaction kettle, a reaction system is decompressed and vacuumized, and inert gas is introduced to the polymerization reaction kettle to reach normal pressure; under the protection of inert gas, heating and adding alkali carbonate, and adding two raw materials of 4, 4-difluorobenzophenone and hydroquinone into the system; the reaction system continues to be heated up for reaction until the pH value of the system is not changed; stirring until the spectrograms of the two on-line infrared spectrograms do not change along with time, synthesizing the target product uniformly, performing repeatable production on the polyaryletherketone product with narrow molecular weight distribution, and obviously improving the market application competitiveness of the product, wherein the product has good batch stability.
Description
Technical Field
The invention relates to a device and a method for repeatable and stable production, in particular to a device and a method for repeatable and stable production of polyaryletherketone with narrow molecular weight distribution, belonging to the field of petrochemical industry.
Background
The development of Polyaryletherketones (PAEK) began in the 60's of the 20 th century, and Du pont, USA, 1962, and ICI, UK, 1964, respectively, reported that polyaryletherketones can be synthesized by electrophilic substitution in the presence of Friedel-Crafts catalysts. Later, there was a significant contribution to the art. In 1979, uk ICI produced high molecular weight PEEK, laying the foundation for the synthesis of polyaryletherketones. The polyaryletherketone mainly comprises Polyetheretherketone (PEEK), Polyetherketone (PEK), Polyetherketoneketone (PEKK), Polyetheretherketoneketone (PEEKK), Polyetherketoneketone (PEKEKK) and the like. Among the major varieties of polyaryletherketones, PEEK is the most important, and was successfully developed by ICI in the United kingdom in 1977 and produced in 1980. By the end of the 80's of the twentieth century, there were mainly 5 major companies in the world producing polyaryletherketones, which were ICI in the United kingdom, Du pont in the United states, Amoco in the United states, BASF in Germany, and Hoechst in Germany, respectively. The development of polyaryletherketones began in the middle of the 80's in the 20 th century, and the university of Jilin in 1990 also disclosed manufacturing patents and had a small production.
Polyether-ether-ketone (PEEK) is a novel semi-crystalline aromatic thermoplastic engineering plastic, not only has high-grade heat resistance, radiation resistance and corrosion resistance, but also has the advantages of excellent dimensional stability, electrical property, excellent processability and the like, and is one of the accepted thermoplastic polymer materials with the highest global performance. The PEEK has wide application fields, and is widely applied to national defense and military industry, aerospace industry, energy development and processing and utilization, automobile manufacturing, electronic information industry and household appliance production. The high-end PEEK product is applied to the fields of medical treatment, health and the like, and has excellent product performance.
Domestic PEEK manufacturers are more and more, the quality of the PEEK produced by the PEEK is different, and the PEEK can meet the requirements after being processed into general downstream PEEK products with low requirements. However, high-end PEEK products are difficult to produce due to the difference between the performance of domestic PEEK materials and the performance of foreign PEEK materials, and still need to be imported in a large quantity. Therefore, the production of domestic high-end PEEK materials has great promotion space.
The difference between the performance of domestic PEEK materials and the performance of foreign PEEK materials is mainly that the PEEK production process is difficult to control, the distribution of the molecular weight of products is too wide due to the instability of production, and the integral performance of the PEEK materials is poor directly. Secondly, the batch stability of PEEK product production is poor, and the PEEK product of the same grade is difficult to be repeatedly and stably produced, so that the market application competitiveness of the product is directly influenced. This is a major technical problem in that the polymerization process is complicated, and the quality of the polymer (e.g., thermal stability, breaking strength, tensile strength, etc.) is closely related to the physical properties of the polymer (e.g., average molecular weight and distribution thereof, average particle diameter and distribution thereof, degree of coarseness, density, etc.). In order to make the polymerization reactor in the best operation condition and improve the quality of the polymer, the traditional means is quality index control, namely, the physical parameters of the polymer or the process parameters related to the physical parameters of the polymer, such as reactant concentration, polymerization rate, conversion rate and the like, are controlled. The most common in the PEEK process is the in-line viscometer. However, the uniformity of macroscopic physical properties does not represent the uniformity of the microstructure of the polymer, resulting in the same large difference in properties of the products, wide molecular weight distribution of the products, and poor reproducibility and stability. In the past, the polymerization product can only be discharged from the polymerization reaction kettle after the reaction is stopped to detect whether the target product requirement is met, and the time is late. Therefore, the improvement of the on-line monitoring and controlling capability of the polymerization process, especially the realization of on-line monitoring of the process of the polymer reaction and the structure of the polymer product becomes the key of the polymer production.
CN 108549903A discloses a quality mode monitoring method for a polymerization reaction process, which can be well used in the production process of PEEK and other polymer materials. However, the method only uses the operating conditions (38 relevant variables such as reaction temperature, initiator concentration, steam flow, pressure, conversion rate, polymerization rate and the like) in the production process of the polymerization reaction as process parameter information related to quality, does not monitor the molecular structure of the product in the reaction process in real time, and cannot directly control the molecular structure of the polymer.
CN103467681A discloses a method for synthesizing a polyetheretherketone resin with high thermal stability, which changes the conventional salt forming agent (sodium bicarbonate), adds a molecular weight regulator, adds a capping agent, and the like to realize the stability of the polyetheretherketone product. However, the method cannot solve the problems that the molecular weight distribution of the product is wide and the product cannot be repeatedly and stably produced from a control point of view.
The CN101104684A patent focuses on the synthesis of a terpolymer PEEK and does not discuss the stability of the molecular weight and the detection and regulation of the repeated productivity of the product.
In conclusion, the repeated stability of PEEK production can be improved only by reinforcing the reaction process of the polymer production process and on-line monitoring of the molecular structure of the polymerization product, so that a PEEK product with narrow molecular weight distribution can be produced, the performance of the PAEK material can be further improved, and a downstream high-end PEEK finished product can be produced, so that the problem that the high-end PEEK depends on import for a long time and is a bottleneck problem is solved, and the method has important significance for the localization of the high-end PEEK.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a device and a method for repeatedly and stably producing polyether-ether-ketone with narrow molecular weight distribution, which have the technical characteristics of repeatedly producing polyether-ether-ketone products with narrow molecular weight distribution, having good product batch stability, remarkably improving the market application competitiveness of the products and the like.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the utility model provides a can real-time supervision reaction process's polymer reactor, includes polymerization reaction kettle, be equipped with the sapphire window of 2 symmetries on polymerization reaction kettle, every the supporting 1 online infrared spectrum probe in sapphire window outside monitors in order to realize polymerization's overall process, online infrared spectrum probe has infrared spectrometer through fiber connection, polymerization reaction kettle embeds there is online pH analysis appearance in order to realize the real-time supervision to polymerization system pH.
Preferably, the online pH analyzer comprises an online pH probe, the online pH probe extends into the polymerization reaction kettle through a flange of the online pH analyzer, and the online pH probe is connected with the online pH analyzer through a transmission line.
Preferably, the top of the polymerization reaction kettle is provided with a first kettle top feeding hole and a second kettle top feeding hole, and the bottom of the polymerization reaction kettle is provided with a kettle bottom discharging hole.
Preferably, a stirring paddle is arranged in the polymerization reaction kettle, a stirring paddle motor is arranged outside the polymerization reaction kettle, and the stirring paddle motor drives the stirring paddle to rotate.
Preferably, a heat conduction oil jacket is arranged at the bottom of the polymerization reaction kettle, and heat conduction oil can be input into the heat conduction oil jacket.
Preferably, the sapphire window is positioned on a flange connected to the polymerization reaction kettle.
The invention relates to a method for repeatedly and stably producing polyaryletherketone with narrow molecular weight distribution, which comprises the following steps:
step 1): adding a reaction solvent diphenyl sulfone into a polymerization reaction kettle, decompressing and vacuumizing a reaction system, and introducing inert gas to normal pressure;
step 2): under the protection of inert gas, heating to 140-160 ℃, adding alkali metal carbonate, and adding two raw materials, namely 4, 4-difluorobenzophenone and hydroquinone, into the system;
step 3): the reaction system is continuously heated and reacts until the pH value of the system is not changed any more;
step 4): stirring until the spectrograms of the two online infrared spectrograms do not change along with the time, and synthesizing the target product uniformly.
Preferably, the molar ratio of the 4, 4-difluorobenzophenone to the hydroquinone is 0.985-1.015: 1.
Preferably, the molar ratio of the hydroquinone to the carbonate is 1: 1.1-1.5.
Preferably, the reaction system temperature-increasing reaction in the step 3) comprises multiple stages, and the first stage is as follows:
heating the reaction system to 200-220 ℃, reacting for 0.5-2.5 hours, if the pH value of the system is not changed, entering the step 4), otherwise, entering the second stage: heating the reaction system to 220-260 ℃, reacting for 0.5-2.5 hours, if the pH value of the system is not changed, entering the step 4), otherwise, entering the third stage: heating the reaction system to 260-290 ℃, reacting for 0.5-2.5 hours, if the pH value of the system is not changed, entering the step 4), otherwise, entering the fourth stage: and heating the reaction system to 300-330 ℃, and reacting for 0.5-5.0 hours until the pH value of the system is not changed.
Has the advantages that: the method can be used for carrying out repeatable production on the polyaryletherketone product with narrow molecular weight distribution, and the product batch stability is good; the prepared polyaryletherketone product has narrow molecular weight distribution, so that the performance of the product can be obviously improved, repeated and stable production can be realized, and the market application competitiveness of the product is obviously improved.
Drawings
FIG. 1 is a schematic view of a polymerization reactor of the present invention.
FIG. 2 is a graph showing the molecular weight distribution of A1 and A2
FIG. 3 is a graph showing the molecular weight distributions of D1 and D2
In the figure: 1-a stirring paddle motor; 2-stirring paddle; 3-sapphire window; 4-an online infrared probe; 5-an optical fiber; 6-infrared spectrometer; 7-flange of on-line pH meter; 8-online pH probe; 9-on-line pH meter; 10-a transmission line; 11-heat conducting oil jacket; 12-a discharge hole at the bottom of the kettle; 13-a first kettle top feed inlet 1; 14-a second kettle top feed inlet 2; 15-polymerization reaction kettle.
Detailed Description
The present invention will be further described with reference to the drawings attached to the specification, but the present invention is not limited to the following examples.
As shown in fig. 1, the embodiment of the polymer reactor capable of monitoring the reaction process in real time includes a polymerization reaction kettle 15, wherein 2 symmetrical sapphire windows 3 are arranged on the polymerization reaction kettle 15, each sapphire window 3 is externally provided with 1 online infrared spectrum probe 4 to monitor the whole polymerization reaction process, the online infrared spectrum probe 4 is connected with an infrared spectrometer 6 through an optical fiber 5, and an online pH analyzer is arranged in the polymerization reaction kettle 15 to monitor the pH of the polymerization reaction system in real time.
The process of the polymer reactor for monitoring the reaction process in real time by adopting the method comprises the following steps:
1) raw materials are respectively added from a first kettle top feeding hole 13 and a second kettle top feeding hole 14, a stirring paddle motor 1 is started, and the stirring paddle motor 1 drives a stirring paddle 2 to rotate;
2) the heat conduction oil can heat the polymerization reaction kettle 15 to a specified reaction temperature through the heat conduction oil jacket 11;
3) at this time, the online infrared probe 4 and the online pH probe can display the reaction state in the polymerization reaction kettle 15 in real time through the infrared spectrometer 6 and the online pH meter 9, respectively;
4) the online infrared probe 4 can monitor the whole process of the polymerization reaction, including the real-time monitoring of the molecular structure of the intermediate product and the molecular structure of the final polymerization product, until the reaction conditions are adjusted to produce a product with a consistent molecular structure of a target product; the on-line pH analyzer arranged in the polymerization reactor can realize real-time monitoring of the pH of the polymerization reaction system until the pH value corresponding to the target product is reached after the reaction is completed.
It should be noted that the processing device such as the infrared spectrometer 6 is adopted in the present application, and should not be understood as a limitation to the characteristics of the software program, and the innovativeness of the present application lies in the connection and arrangement of the structures.
In a preferred embodiment mode, the online pH analyzer comprises an online pH probe 8, the online pH probe 8 extends into a polymerization reaction kettle 15 through a flange 7 of the online pH analyzer, and the online pH probe 8 is connected with an online pH meter 9 through a transmission line 10.
In a preferred embodiment, the top of the polymerization reactor 15 is provided with a first reactor top feed inlet 13 and a second reactor top feed inlet 14, and the bottom of the polymerization reactor 15 is provided with a reactor bottom feed outlet 12.
In a preferred embodiment mode, a stirring paddle 2 is arranged in the polymerization reaction kettle 15, a stirring paddle motor 1 is arranged outside the polymerization reaction kettle 15, and the stirring paddle motor 1 drives the stirring paddle 2 to rotate.
In a preferred embodiment, a heat-conducting oil jacket 11 is arranged at the bottom of the polymerization reaction kettle 15, and heat-conducting oil can be input into the heat-conducting oil jacket 11.
In a preferred embodiment, the sapphire window 3 is located in a flange attached to the polymerization reactor 15.
The invention relates to a method for repeatedly and stably producing polyaryletherketone with narrow molecular weight distribution, which comprises the following steps:
step 1): adding a reaction solvent diphenyl sulfone into a polymerization reaction kettle 15, decompressing and vacuumizing a reaction system, and introducing inert gas to normal pressure;
step 2): under the protection of inert gas, heating to 140-160 ℃, adding alkali carbonate, and adding two raw materials of 4, 4-difluorobenzophenone and hydroquinone into the system;
and step 3): the reaction system is continuously heated and reacts until the pH value of the system is not changed any more;
step 4): stirring until the spectrograms of the two on-line infrared spectrograms do not change along with the time, and synthesizing the target product uniformly.
Preferably, the molar ratio of the 4, 4-difluorobenzophenone to the hydroquinone is 0.985-1.015: 1.
Preferably, the molar ratio of the hydroquinone to the carbonate is 1: 1.1-1.5.
Preferably, the reaction system temperature-increasing reaction in the step 3) comprises multiple stages, and the first stage is as follows:
heating the reaction system to 200-220 ℃, reacting for 0.5-2.5 hours, if the pH value of the system is not changed, entering a step 4), otherwise, entering a second stage: heating the reaction system to 220-260 ℃, reacting for 0.5-2.5 hours, if the pH value of the system is not changed, entering the step 4), otherwise, entering the third stage: heating the reaction system to 260-290 ℃, reacting for 0.5-2.5 hours, if the pH value of the system is not changed, entering the step 4), otherwise, entering the fourth stage: and heating the reaction system to 300-330 ℃, and reacting for 0.5-5.0 hours until the pH value of the system is not changed.
Example 1
Diphenylsulfone solvent (336kg) was added to a special polymerization reactor with a sapphire window 3, an online infrared probe 4 and an online pH analyzer. Vacuum-pumping 0.2MPa under reduced pressure, and introducing nitrogen to normal pressure. The mixture was heated to 160 ℃ under nitrogen. Sodium carbonate (63.6kg), 4-difluorobenzophenone (109.0kg) and hydroquinone (55.6kg) were added. The reaction kettle is heated to 220 ℃ for reaction for 1.5 hours, 250 ℃ for reaction for 0.5 hours, 290 ℃ for reaction for 0.5 hours, and heated to 320 ℃, and stirring is continued until the pH value does not change, but the spectrogram of the online infrared spectrum changes along with the time, and stirring is continued for about 30 minutes until the two infrared spectrograms do not change along with the time.
Discharging the polymer solution on a cold steel plate, cooling and crushing. Adding 600kg ethanol, boiling for 30 min, and filtering. The ethanol washing and filtering process was repeated 5 times. Drying at 80 ℃ for 3 hours. Adding 600kg of distilled water, boiling, filtering, repeatedly washing for 7 times, and drying at 140 ℃ for 6 hours. The product is designated A1 and the DSC and tensile properties are shown in Table 1.
Example 2
The procedure of example 1 was repeated to demonstrate good reproducibility (as shown in FIG. 2). The method comprises the following specific operations: diphenylsulfone solvent (336kg) was added to a special polymerization reactor with a sapphire window 3, an online infrared probe 4 and an online pH analyzer. Vacuum-pumping 0.2MPa under reduced pressure, and introducing nitrogen to normal pressure. Heating to 160 ℃ under nitrogen protection. Sodium carbonate (63.6kg), 4-difluorobenzophenone (109.0kg) and hydroquinone (55.6kg) were added. The reaction kettle is heated to 220 ℃ for reaction for 1.5 hours, 250 ℃ for reaction for 0.5 hours, 290 ℃ for reaction for 0.5 hours, and heated to 320 ℃, and stirring is continued until the pH value does not change, but the spectrogram of the online infrared spectrum changes along with the time, and stirring is continued for about 30 minutes until the two infrared spectrograms do not change along with the time.
Discharging the polymer solution on a cold steel plate, cooling and crushing. Adding 600kg ethanol, boiling for 30 min, and filtering. The ethanol washing and filtering process was repeated 5 times. Drying at 80 deg.C for 3 hr. Adding 600kg of distilled water, boiling, filtering, repeatedly washing for 7 times, and drying at 140 ℃ for 6 hours. The product is designated A2 and its DSC and tensile properties are shown in Table 1.
Comparative example 1
The reaction procedure of example 1 was followed, but the reaction was carried out using a conventional stirred polymerization vessel to which was added diphenylsulfone solvent (336 kg). Vacuum-pumping 0.2MPa under reduced pressure, and introducing nitrogen to normal pressure. The mixture was heated to 160 ℃ under nitrogen. Sodium carbonate (63.6kg), 4-difluorobenzophenone (109.0kg) and hydroquinone (55.6kg) were added. The temperature of the reaction kettle is increased to 220 ℃ for reaction for 1.5 hours, the temperature of the reaction kettle is increased to 250 ℃ for reaction for 0.5 hour, the temperature of the reaction kettle is increased to 320 ℃ for reaction for 0.5 hour, and the stirring is continued for about 45 minutes until the reading of the on-line viscometer is constant.
Discharging the polymer solution on a cold steel plate, cooling and crushing. Adding 600kg ethanol, boiling for 30 min, and filtering. The ethanol washing and filtering process was repeated 5 times. Drying at 80 ℃ for 3 hours. Adding 600kg of distilled water, boiling, filtering, repeatedly washing for 7 times, and drying at 140 ℃ for 6 hours. The product is designated D1 and its DSC and tensile properties are shown in Table 1.
Comparative example 2
The procedure of comparative example 1 was repeated to demonstrate the poor reproducibility of the prior art. The method comprises the following specific operations: the reaction procedure of example 1 was followed, but the reaction was carried out using a conventional stirred polymerization vessel to which a diphenylsulfone solvent (336kg) was added. Vacuum-pumping 0.2MPa under reduced pressure, and introducing nitrogen to normal pressure. Heating to 160 ℃ under nitrogen protection. Sodium carbonate (63.6kg), 4-difluorobenzophenone (109.0kg) and hydroquinone (55.6kg) were added. The reaction kettle is heated to 220 ℃ for reaction for 1.5 hours, 250 ℃ for reaction for 0.5 hours, 290 ℃ for reaction for 0.5 hours, and heated to 320 ℃, and the stirring is continued for about 45 minutes until the reading of the on-line viscometer is constant.
Discharging the polymer solution on a cold steel plate, cooling and crushing. Adding 600kg ethanol, boiling for 30 min, and filtering. The ethanol washing and filtering process was repeated 5 times. Drying at 80 ℃ for 3 hours. Adding 600kg of distilled water, boiling, filtering, repeatedly washing for 7 times, and drying at 140 ℃ for 6 hours. The product at this point is designated D2 and its DSC and tensile test results are shown in Table 1.
Table 1 gives the analysis of the properties of the polymers
T by the polymers in Table 1gThe comparison of the properties of the melting point and the tensile strength shows that the PEEK products A1 and A2 prepared by the method have good repeatability and stability of the properties, and the stretching of the materialsThe strength is also significantly improved. T of D1 and D2 for comparative examplegPoor repeatability of properties of melting point and tensile strength. Further illustrates that the method of the invention can effectively produce the polyether-ether-ketone product with narrow molecular weight distribution in a repeatable way, and the product has good batch stability.
The molecular weight distribution curves are given in FIG. 2 and FIG. 3, respectively. As can be seen from the figure, the molecular weight distribution curves of A1 and A2 are narrow, almost overlapped and have good repeatability; the molecular weight distributions of D1 and D2 were broad and did not overlap, indicating poor reproducibility.
Finally, it is noted that the present application also includes embodiments where the endpoints of the range value (the embodiment formed by the front endpoints, the embodiment formed by the intermediate values, and the embodiment formed by the back endpoints) are taken separately. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (10)
1. An apparatus for repeatable and stable production of polyaryletherketone with narrow molecular weight distribution comprises a polymerization kettle (15), and is characterized in that: be equipped with sapphire window (3) of 2 symmetries on polymerization reaction kettle (15), every sapphire window (3) outside 1 online infrared spectrum probe (4) monitor in order to realize polymerization's overall process, online infrared spectrum probe (4) are connected with infrared spectrometer (6) through optic fibre (5), polymerization reaction kettle (15) embeds there is online pH analysis appearance in order to realize the real-time supervision to polymerization system pH.
2. The apparatus of claim 1, wherein the apparatus for repeatable and stable production of narrow molecular weight distribution polyaryletherketones comprises: the online pH analyzer comprises an online pH probe (8), the online pH probe (8) extends into the polymerization reaction kettle (15) through a flange (7) of the online pH analyzer, and the online pH probe (8) is connected with an online pH meter (9) through a transmission line (10).
3. The apparatus for repeatable and stable production of narrow molecular weight distribution poly (aryl ether ketone) s of claim 1 or 2, wherein: a first kettle top feeding hole (13) and a second kettle top feeding hole (14) are formed in the top of the polymerization reaction kettle (15), and a kettle bottom discharging hole (12) is formed in the bottom of the polymerization reaction kettle (15).
4. The apparatus of claim 1, wherein the apparatus is capable of repeatable and stable production of polyaryletherketones with narrow molecular weight distribution, and comprises: the polymerization reaction kettle (15) is internally provided with a stirring paddle (2), the polymerization reaction kettle (15) is externally provided with a stirring paddle motor (1), and the stirring paddle motor (1) drives the stirring paddle (2) to rotate.
5. The apparatus of claim 1, 2 or 4, wherein the apparatus comprises: the bottom of the polymerization reaction kettle (15) is provided with a heat conduction oil jacket (11), and heat conduction oil can be input into the heat conduction oil jacket (11).
6. The apparatus of claim 1, wherein the apparatus for repeatable and stable production of narrow molecular weight distribution polyaryletherketones comprises: the sapphire window (3) is positioned on a flange connected with a polymerization reaction kettle (15).
7. A method for repeatedly and stably producing polyaryletherketone with narrow molecular weight distribution is characterized by comprising the following steps:
step 1): adding a reaction solvent diphenyl sulfone into a polymerization reaction kettle (15), decompressing and vacuumizing a reaction system, and introducing inert gas to normal pressure;
step 2): under the protection of inert gas, heating to 140-160 ℃, adding alkali metal carbonate, and adding two raw materials, namely 4, 4-difluorobenzophenone and hydroquinone, into the system;
and step 3): the reaction system is continuously heated and reacts until the pH value of the system is not changed any more;
step 4): stirring until the spectrograms of the two on-line infrared spectrograms do not change along with the time, and synthesizing the target product uniformly.
8. The method of claim 7, wherein the method comprises the steps of: the molar ratio of the 4, 4-difluorobenzophenone to the hydroquinone is 0.985-1.015: 1.
9. The method of claim 7 or 8, wherein the method comprises the steps of: the molar ratio of the hydroquinone to the carbonate is 1: 1.1-1.5.
10. The method of claim 7, wherein the method comprises the steps of: the temperature rising reaction of the reaction system in the step 3) comprises multiple stages, wherein the first stage comprises the following steps: heating the reaction system to 200-220 ℃, reacting for 0.5-2.5 hours, if the pH value of the system is not changed, entering a step 4), otherwise, entering a second stage: heating the reaction system to 220-260 ℃, reacting for 0.5-2.5 hours, if the pH value of the system is not changed, entering the step 4), otherwise, entering the third stage: heating the reaction system to 260-290 ℃, reacting for 0.5-2.5 hours, if the pH value of the system is not changed, entering the step 4), otherwise, entering the fourth stage: the temperature of the reaction system is increased to 300-330 ℃, and the reaction is carried out for 0.5-5.0 hours until the pH value of the system is not changed.
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| CN106188523A (en) * | 2016-07-20 | 2016-12-07 | 汤原县海瑞特工程塑料有限公司 | A kind of method preparing PAEK base polymer |
| CN217605651U (en) * | 2022-03-02 | 2022-10-18 | 双驱智能科技(宁波)有限公司 | Polymer reactor capable of monitoring reaction process in real time |
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| CN1245570A (en) * | 1996-12-31 | 2000-02-23 | 埃克森化学专利公司 | On-line control of chemical process plant |
| US6635224B1 (en) * | 1998-10-30 | 2003-10-21 | General Electric Company | Online monitor for polymer processes |
| WO2000049395A1 (en) * | 1999-02-18 | 2000-08-24 | Rhodia Chimie | Method for preparing latex by emulsion (co)polymerisation of ethylenically unsaturated monomers, with direct inline monitoring by raman spectroscopy |
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